US3186968A - Polymeric compositions resistant to ultra-violet light from acrylyloxymethyl benzoates - Google Patents

Polymeric compositions resistant to ultra-violet light from acrylyloxymethyl benzoates Download PDF

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Publication number
US3186968A
US3186968A US150197A US15019761A US3186968A US 3186968 A US3186968 A US 3186968A US 150197 A US150197 A US 150197A US 15019761 A US15019761 A US 15019761A US 3186968 A US3186968 A US 3186968A
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ultra
violet
phenyl
benzoate
hydroxy
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US150197A
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Fertig Joseph
Skoultchi Martin
Albert I Goldberg
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Ingredion Inc
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National Starch and Chemical Corp
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Priority to US150197A priority patent/US3186968A/en
Priority to GB38792/62A priority patent/GB980888A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F20/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F20/02—Monocarboxylic acids having less than ten carbon atoms, Derivatives thereof
    • C08F20/10—Esters
    • C08F20/12—Esters of monohydric alcohols or phenols
    • C08F20/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms

Definitions

  • This invention relates to polymeric compositions and to the process for their preparation, and more particularly to polymers and copolymers displaying unusual resistance to the degradative eifects'of ultra-violet radiation It is the prime object of this invention to provide polymeric compositions derived from monomeric materials whose presence imparts vastly improved light stability to the resulting polymers.
  • An additional object of this invention involves the preparation of polymers which withstand the effects of ultra-violet light without the necessity of their being formulated with any extraneous ultra-violet light absorbers.
  • ultra-violet light absorbers in the synthetic plastics derived from high polymers is, of course a practice well known to those skilled in the art. Such ultra-violet absorbers are required since outdoor exposure to natural sunlight or continuous indoor exposure to fluorescent light tends to degrade most plastics and this photodegradation of plastics is, in turn, known to be caused by the ultra-violet portion of light. Such degradation is observable in a plastic as a result of a. change in color, such as a yellowing or dark ening, and/ or by a deterioration of its physical properties, such as its fiexural strength.
  • ultra-violet absorbers or stabilizers such as the phenyl salicylates or the ortho-hydroxy benzophenones
  • phenyl salicylates or the ortho-hydroxy benzophenones have of late become of considerable commercial interest.
  • such materials should be able to absorb strongly in the ultra-violet range of from 300-400 millimicrons without undergoing any change in structure.
  • they must possess many other properties such as low color, good compatibility, heat stability, low odor, low volatility, chemical stability and chemical inertness.
  • phenyl ortho-hydroxy henzoate esters such as phenyl salicylate
  • phenyl salicylate have many advantages as ultra-violet absor-bers. They are colorless, relatively inexpensive and moderately elfective, particularly in the range of about 350 millimicrons or higher. However, their compatibility varies depending upon the specific benzoate ester and the plastic with which they are used. Thus, they may be somewhat volatile, impart odor and, under certain conditions they may give rise to the problems of toxicity and migration.
  • novel polymeric compositions of our invention are thus found to possess all of the many advantages, and particularly the improved light stability, which results from'the ultilization of extraneous ultra-violet light absorbers while managing to avoid all of the problems which are normally associated with their use.
  • This improved light stability is imparted to these polymers as a result of the presence therein of the phenyl ortho-hydroxy benzoate moiety which is permanently bound into and inherently part of the resulting polymer molecules as a result of the incorporation therein of these ethylenically unsaturated phenyl orthohydroxy benzoate monomers.
  • the products of our invention may thus be said to comprise those homoand copolymers containing at least one ethylenically unsaturated phenyl or substituted phenyl salicylate derivative corresponding to the formula:
  • X represents an ethylenically unsaturated group selected from the class consisting of acrylyloxy, acrylyloxyalkyl, methacrylyloxy, and methacrylyloxyalkyl groups and Y and Z represents at least one member of the classconsisting of hydrogen, alkyl, aryl, acyloxy, aralkyl, or halogen radicals.
  • phenyl 2-hydroiry-4-acr'ylyloxy benzoate As representative of the above described monomers containing the phenyl salicylate moiety, one may list phenyl 2-hydroiry-4-acr'ylyloxy benzoate; phenyl 2-hydroxy-5-acrylyloxy benzoate; phenyl 2-hydroxy-5-acrylyloxymethyl benzoate; phenyl 2-hydroxy-4-methacry1yloxy benzoate; phenyl Z-hydroxy-S-methacrylyloxy benzoate; and, phenyl Z-hydroxy-S-methacrylyloxymethyl benzoate.
  • the monomers which are essential for the preparation of the polymeric compositions of our invention may be described as the acrylyloxy, methacrylyloxy, acrylyloxyalkyl and methacrylyloxyalkyl derivatives of phenyl salicylate.
  • Each of the above listed monomeric derivatives may, in turn, contain a variety of other substituent groups including halogen, alkyl, aryl, acyloxy, and aralkyl groups wherein these latter groups may be substituted on either of the phenyl rings in the phenyl salicylate moiety.
  • the cornonomers which may be utilized together with the above described ethylenically unsaturated phenyl salicylate derivatives for the preparation of the ultraviolet stable compositions of our invention can be any ethylenically unsaturated monomer such, for example, as styrene; methyl styrene; the -acrylic and methacrylic acid esters of aliphatic alcohols such as methyl, ethyl, propyl, butyl, isobutyl, hexyl, 2-ethyl hexyl, octyl, lauryl and stearyl alcohols; acrylic acid; methacrylic acid; acrylradiation, the copolymers of our invention should containat least 0.2%, by weight, of these ethylenically unsaturated phenyl salicylate derivatives.
  • any I of the usual vinyl polymerization methods which are well known to those skilled in the art.
  • they may be prepared by means of free radical initiated processes utilizing bulk, suspension, solution, or emulsion polymerization techniques; or, they may beiprepared by ionic catalysis or by means of stereospecific catalysts such as those of the type developed by Ziegler.
  • Such copolymers may, if compatible, be directly blended with the cellulosics or sparvarnishes and thereby impart the advantages of the compositions of our invention to these materials;
  • ultra-violet stabilizers are polyesters, polystyrene, polyvinyl chloride, polyethylene and polyvinylidene chloride.
  • Polyesters namely, the unsaturated polyesters having 'ethylenic unsaturation resulting from the presence of alpha, beta-unsaturated carboxylic acids such asmaleic andv fumaric acid, are typically formulated with monomeric styreneor methyl methacrylate and, in' conjunction withfiber glass reinforcement, are employed in the preparation of corrugated andflat sheeting products. The latter are used as roofings, awnings, walk coverings,
  • polyester resins tend to yellow and physically deteriorate.
  • the practitioner need merely introduce one of the'above described phenyl salicylate monomers together with the styrene or methyl methacrylate monomer, the polymerization catalyst and the unsaturated poly,-
  • polystyrene has beenreoommended as a plastic for automobile reflector lights and indoor light diffusing louvers.
  • polystyrene on exposure to either natural or fluorescent light tends to discolor and crack within a short period of time.
  • the resulting homogeneous copolymer is found to be remarkably resistant to both natural and fluorescent light.
  • Polyvinyl chloride and vinyl chl-oridecopolymer film formulations tend to discolor and become embrittled .When exposed to light for prolonged periods of time.
  • Example I This example illustrates the preparation of one of the novel copolymers of our invention and also demonstrates its improved resistance to the degradative'efiects of ultraviolet rad fition. i p
  • An aqueous ylatex of a 90:8 :2 vinylidene-chloride: ethyl acrylatez phenyl Z-hydroxy-S-acrylyloxymethyl benzoate erpolyme'r' was prepared by charging the following ingredients into, a reactor equipped with a reflux condenser aswell as with means for mechanical agitation.
  • This latex' was then used in the preparation of 1.5 mil (dry thickness) coatings which were cast upon sheets of white paper.
  • Various samples of these coated sheets I were then exposed to the following lights sources: (A) At a distance of 6" to a 15 .Watt ultra-violet germicidal lamp havmga radiation range of 220-400 inillimicrons; (B) at a distance of 3" to four 20 watt fluorescent bulbs which were enclosed, together with the test sheets, within a sealed box; (C). to sunlight. As controls for these tests, similarly' coated sheets were exposed under the identical con-.
  • control sheets were derived, in one case, from a 90: vinylidene chloridezethyl acrylate copolymer latex which had been polymerized in the presence of 2% of phenyl salicylate, as based upon the total weight of the monomers.
  • the coatings of the second set of control sheets were derived from a 90: 10 vinylidene chloridezethyl acrylate copolyrner latex.
  • Control comprising vinylidene ehloridezethyl acrylate copoiyrner 40. 5 21. 5
  • Example 11 This example illustrates the preparation of one of the novel copolymers of our invention and also demonstrates its improved resistance to the degradative effects of ultraviolet radiation.
  • An aqueous latex of a 90:8:2 vinylidene chloridezethyl acryla-te:phenyl 2 hydroxy 4 acrylyloxy benzoat terpolymer was prepared using the same ingredients and by means of the same procedure used for the preparation of the terpolymer latex of Example I with the exception, in this instance, that phenyl 2-hydroxy-4-acrylyloxy benzoate was used as the ultra-violet absorbing monomer.
  • the resulting latex had a resin solids content of 50%, by Weight, and an intrinsic viscosity of 0.8, when measured in tetra hydrofur-an at 22 C.
  • Example III This example illustrates the preparation of one of the novel copolymers of our invention and also demonstrates its improved resistance to the degradative efiects of ultraviolet radiation.
  • An aqueous latex of a 7 4:24:2 vinylidene chloridezbutyl acrylatezphenyl 2-hydroxy-S-acrylyloxymethyl benzoate terpolymer was prepared by charging the following ingradients into a reactor equipped with a reflux condenser and means for mechanical agitation.
  • This latex was then used in the preparation of 1.5 mil (dry thickness) coatings which were cast upon sheets of white paper. Samples of these coated sheets were then exposed for 24 hours to the ultra-violet germicidal lamp.
  • the controls for this test comprised sheets which had been coated with a 74:26 vinylidene chloridezbutyl ac rylate copolymer latex. The effects of this exposure to an ultra-violet source were evaluated with a Photovolt Reflectometer and the following table presents the results of these tests.
  • Example IV This example illustrates the preparation of one of the novel copolymers of our invention and also demonstrates its improved resistance to the degradative effects of ultraviolet radiation.
  • An aqueous latex of a 69:29:2 vinyl chloridezoctyl acrylatezphenyl 2-hydroxy-S-acrylyloxymethyl benzoate terpolymer was prepared by charging the following ingredients into a pressurized reactor.
  • This latex was then used in the preparation of 1.5 mil (dry thickness) coatings which were cast upon sheets of White paper. Samples of these coated sheets were then exposed for 28 days to the ultra-violet germicidal lamp.
  • the controls for this test comprised sheets which had been coated with a 70:30 vinyl chloridemctyl acrylate copolymer latex. The effects ofthis exposure to an ultraviolet source were evaluated with a Photovolt Reflectometer and the following presents the results of these tests.
  • Control comprising vinylidene chloridezoctyl acrylate copolymer 27.5
  • aqueous latex of a 6822824 vinyl chloride:octyl acrylatezphenyl 2-hydroxy-S-acrylyloxymethyl benzoate terpolymer was prepared using the same, ingredients and 3 novel homopolymers of our invention and also demon-' white paper. Samples of these coated sheets were then exposed for 28 days to the ultra-violet germicidal lamp.
  • the controls for this test comprised sheets which had been coated with a 70:30 vinyl chloridezoctyl acrylate copolymer latex. The eflects of this exposure to an ultraviolet source were evaluated with a Photovolt Reflector-neter and the following table presents the results of these tests.
  • Example VI v This example illustrates the preparation of one of the novel copolymers of our invention and also demonstrates its. improved resistance tothe degradative effects of ultraviolet'radiation;
  • Example VII 7 7 This example illustrates the preparation of one of the strates its use as a protective coating for an ultra-violet sensitive polymer. Evidence of the prolonged stability of this homopolymer to ultra-violet radiation is also given.
  • An ethyl acetate lacquer of polyphenyl Z-hydroxy-S- acrylyloxymethyl benzoate was prepared by charging the flux condenser and means for mechanical agitation.
  • Example VIII This example illustrates the preparation of one of the novel copolymers of our invention and also demonstrates its use as a protective coating for an ultra-violet sensitive polymer.
  • An ethyl acetate lacquer of a 74:26 phenyl 2-hydroxy- S-acrylyloxy benzoatezmethyl acrylate copolymer was prepared by charging the following ingredients into a reactor equipped with a reflux condenser and means for mechanical agitation.
  • a composition comprising a polymer of at least one ethylenically unsaturated monomer selected from the group consisting of styrene, methyl styrene, the acrylic and methacrylic acid esters of aliphatic alcohols, acrylic acid, methacrylic acid, acrylamide, acrylonitrile, methacrylonitrile, vinylidene chloride, vinyl chloride, vinyl acetate, ethylene and propylene together with at least one ethylenically unsaturated phenyl salicylate derivative selected from the group consisting of phenyl Z-hydroxy- S-acrylyloxymethyl benzoate and phenyl 2-hydroxy-5- methacrylyloxymethyl benzoate.
  • a copolymcr in accordance with claim 1, of vinylchloride, octyl acrylate and phenyl 2-hydroxy-5-acrylyloxyrnethyl benzoate.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Graft Or Block Polymers (AREA)
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US150197A 1961-11-06 1961-11-06 Polymeric compositions resistant to ultra-violet light from acrylyloxymethyl benzoates Expired - Lifetime US3186968A (en)

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NL285142D NL285142A (enrdf_load_stackoverflow) 1961-11-06
US150197A US3186968A (en) 1961-11-06 1961-11-06 Polymeric compositions resistant to ultra-violet light from acrylyloxymethyl benzoates
GB38792/62A GB980888A (en) 1961-11-06 1962-10-12 Improvements in or relating to polymers resistant to ultra-violet light

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328491A (en) * 1964-05-01 1967-06-27 Nat Starch Chem Corp Uv light absorbing copolymers of acryloxymethyl benzoates and dihydroxybenzophenone derivatives
US3445566A (en) * 1966-03-18 1969-05-20 Nat Starch Chem Corp Hair spray compositions containing an ultraviolet absorbing film forming copolymer
US3483162A (en) * 1967-04-25 1969-12-09 Sperry Rand Corp Photochromic schiff base copolymers
US4719248A (en) * 1985-08-08 1988-01-12 Bausch & Lomb Incorporated Ultraviolet blocking agents for contact lenses

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2545044A (en) * 1947-11-22 1951-03-13 Eastman Kodak Co Method of preparing an alpha-methacryloxy propionamide
US2910454A (en) * 1956-08-02 1959-10-27 Dow Chemical Co Hydrocarbon polymers stabilized with b-resorcylic acid diesters
US2938883A (en) * 1956-11-19 1960-05-31 Dow Chemical Co Chloroethylene polymers stabilized with monoacrylic esters of hydroxy phenones
US3113907A (en) * 1963-12-10 Polymeric compositions and preparation
US3141903A (en) * 1961-11-06 1964-07-21 Nat Starch Chem Corp Ethylenically unsaturated phenyl salicylate derivatives

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3113907A (en) * 1963-12-10 Polymeric compositions and preparation
US2545044A (en) * 1947-11-22 1951-03-13 Eastman Kodak Co Method of preparing an alpha-methacryloxy propionamide
US2910454A (en) * 1956-08-02 1959-10-27 Dow Chemical Co Hydrocarbon polymers stabilized with b-resorcylic acid diesters
US2938883A (en) * 1956-11-19 1960-05-31 Dow Chemical Co Chloroethylene polymers stabilized with monoacrylic esters of hydroxy phenones
US3141903A (en) * 1961-11-06 1964-07-21 Nat Starch Chem Corp Ethylenically unsaturated phenyl salicylate derivatives

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3328491A (en) * 1964-05-01 1967-06-27 Nat Starch Chem Corp Uv light absorbing copolymers of acryloxymethyl benzoates and dihydroxybenzophenone derivatives
US3445566A (en) * 1966-03-18 1969-05-20 Nat Starch Chem Corp Hair spray compositions containing an ultraviolet absorbing film forming copolymer
US3483162A (en) * 1967-04-25 1969-12-09 Sperry Rand Corp Photochromic schiff base copolymers
US4719248A (en) * 1985-08-08 1988-01-12 Bausch & Lomb Incorporated Ultraviolet blocking agents for contact lenses

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NL285142A (enrdf_load_stackoverflow)

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